Process of making low-boiling hydrocarbons



APPLICATION FILED MAR. 14, 1916.

. Patented Apr. 4, 1922.

UNITED s'ra'ras PATENT OFFICE.

cmvn M. or PORT ARTHUR, ems, AssIeNon. r0 GULF nun-mine I COMPANY, OFQP'I TTSBURGH, PENNSYLVANIA, A CORPORATION OF TEXAS.

' rnocnss ormme LOW-BOILING nypnocaanons.

. Application inea March 14,1616. Serial No. 84,211..

To all whom it may concern: 1

- -Be it known that I, CLIVEM. ALEXANDER, a citizen of the. United States, residing at Port Arthur, in the county of J efl'erson and State of Texas, have invented certain new hydrocarbon oils, such as gasoline, benzol, toluol, etc., but more particularly benzol and toluol, wherein oil gas from any suitablesource, oil-containing gas, such as the natural gases from which casing head gasoline, is obtained, etc.,.is submitted to a high heat -under a comparatively high pressure; as

by taking natural gas, still gases, gases made by heating oil, etc., placing the gas under a pressure of, say, 50 to 100 or more pounds and heating to a suitable temperature to propressure, produced in the cracking distilla-1 duce decomposition of the gas with rearrangement thereof to form vapors of low boiling or .liquefiable hydrocarbons, such temperature being advantageously between, say, 500 and 1000 0.; all as.more, fully hereinafter set forth and as claimed.

' In view of the present active demand for low boiling h drocarbon oils, both of the' nature of gaso ine and of that of benzol and toluol, for various purposes there has been an active search for new sources of these bodies. I have found that by taking the permanent gases, that is the gases which are;

permanent at the ordinary temperature and ti'on of the oil, and heating such gases under heavy pressure, I can produce therefrom by molecular rearrangement various low boiling oils useful in the arts. By heating to a comparatively low temperature, say, about 500 to 750 C.under 50'to 100 pounds pres- ,sure'and then cooling, theloils produced will be largely of'a petroleum character; i. e.,

xwill be gasoline, and to some extent kerosene. By using a higher temperature I can produce aromatic low boiling oils of the nature of benzol'and toluol operation a somewhat higher pressure is useful; say up to 150 or 200 pounds.

Oil gas from a variety of sources maybe.

employed for these processes. 'I may'make the oil gas from the cheaper forms of petroleum and petroleum products by passing the In this. latter Specification of Letters Patent. ,Patent d A 4, 1922 same or the vapors thereof through a heatmg zone,-such as a hot tube, at a temperature of 700 to 1000 (1.; but preferably for the may be both compressed and scrubbed with oil. I am not restricted this operation to the use of oil gas coming from breaking down oil since I may also use various natural gases of the same type containing more or less liquefiable components; the type of natural gas yielding what is known as casing head gasoline. This type of natural gas is particularly advatageous in the present process. The dry natural, gases, consisting mainly of methane, do not yield so readily to this treatment. V l Any suitable apparatus may be employed in'the performance of the described process. -I ordinaril "take the gas and free. it of liquefiable ydrocarbon oils by cooling or compressing or both and thereafter deliver it under heavy pump pressure, using any suitable type of' pu'mp, to a heated zonethrough which it is passed. under pressure. This heating zone may be a tubular retort of any desired structure of"any suitable ma terial. Iron or steel piping is perfectly suitable. Any suitable means of heating, such as flameheating, electric heating, etc., may be employed; The temperature of the heating zone should ,bebetween 500 and 1000 C.; the'particular temperature emplo ed depends upon the time of heating a orded. Catalysts may or -may not be'present. Their presence is often,useful as lowering the necessary heat and pressure. Mo'st of the commonmetals ave the power of catalyzing or facilitating the.operation.- Coppen, nickel, cobalt, iron, etc., or their oxids may be used. Inorder to present a larger surfacefor action and to distribute the heat more uniformly, the heating zone may beprovidedwith a' charge of an inert carriering condensed therein under pressure or not as the case may be. It is advantageous to pass the gases and vapors preliminarily through an air cooled condenser of limited extent to cause a preliminary deposition of tar and then pass the gases through'an ordinary water cooled condenser of any desired type. 'By placing a reducing valve beyond the condenser the condensation may beeffected under the pressure of the system.

This is useful as causing the condensate to take up some of the-more volatile liquefiable products formed in the action; and is particularly. useful when the process is applied to the manufacture of gasoline.

. densed product may be refractionated in '-ratu s useful in the performance of my In making benzol and 'toluol, the 'conany suitable type of distilling apparatus.

In one specific embodiment of my invention I take the gases coming from any ordinary cracking still,' ,compress these gases at, say, 100 pounds pressure, and cool as by water cooling, removing an liquid which may form in this cooling\ he cooled gases still under pressure are then transmitted through a heated steel tube kept at a temperature between 500 and 1000 C.; the

higher temperatures being better adapted to The the manufacture of low boiling, aromatic oils'while the lower temperatures are better adapted for the manufacture of gasoline. (gases coming from .the hot 'tube are coole scribed. v v

In'lieu of using the described permanent gases in amodification of the resent invention the more volatile norma ly liquid hydrocarbons, say those that are liquefiable at temperatures below 50 C. may be employed By cooling and'condensing certain types of natural gas, a mixture of 'very' volatile low boiling hydrocarbons is obtained; many of these mixtures boilin at the heat of the air. These wild gaso mes are 'not highly desirable for commercial purposes because of the difliculty in handling them; some gradesindeed it is impossible to ship by rail under-the ordinary legal restrictions. By passing gas- "olines' of this type through the heated zone in the sairie manner as described for permanent' gases more valuable liquefiable products 'of the nature of ordinary gasoline are obtained. Thesewery low boiling gasolines gas, casm and otherwise treated as just demay be converted either intoordinary gasoline or into low boiling aromatic oils as the (casing head gas), without separating condensable vapors therefrom, and submit it to heat and pressure in the described manner. i In the described operation in treating oil head. gas, etc., under heat and pressure, dilute the gas going into the heated zone with more or less of the gas which has already been treated and which had been freed of liquefiable constituents by cooling. This gas contains more or less hydrogen and under the familiar rule its presence tends to restrain the formation of more hydrogen; and to cause the hydrocarbon oils produced tobe of less unsaturated material. The effect of ture prior to the return in orderto prod more free hydrogen there find it is often advantageous to.

In the accompanying drawing I have shown more'or less diagrammatically, partly in elevation and partly in section, an appaprocess.

In the, drawings, element 1 is the fire chamber of a still 2 heated by means of the burners-3 and 4. Exhaust gases escape at liminaryl'air cooled con enser 9 which is" provided with aback trap 10 to return heavy condensates to the still for further operation. From the air cooled condenser 9 the vapors pass through valved pipe 11 to the water cooled condenser 12. This condenser is provided with inlet ,13 and outlet 14 for the water. .Uncondensed gases and vapors pass through valvedv line 15 to the compresser 16'or may if desiredbe passed through lines 31 and 30 to join the pipe 20 on the pressure side of the compresser. When vapors or gases from another source, as for instance casing head gasoline from a well, is to be operated upon, it is sent Through ipe 18 and pipe 17 to the compresser 16.

pass through line 25 to the air cooled condenser 26 from which heavy oils condensed may bewithdrawn for use. Uncondensed rom 16 the vapors and gases which have passed .the condenser 12" or the vapors and gases which have been Condensates are collected at 19.

vapors and gases pass this air cooled con- 1 denser through valved line 27 to the water cooled Condenser 28. The condensate from the water cooled condenser may be Withdrawn at 29. The uncondensed vapors and gasesmay be sent back to the cracking tube I 21 through line 30 on the pressure s1de of oils which comprises passing permanent gases from a petroleum source through a heated zone at a temperature between 500 and 1000 C. and under heavy pressure, cooling theefliuent gases and condensing liquefiable hydrocarbons formed.

2. The process of produclng volatilelow boiling oils which comprises heating gaseous hydrocarbons from a petroleum source having boiling point slower than the boiling points of the oil to be'produced to a temperature between 500 and 1000 C. under heavy pressure, cooling the gases and vapors resulting from such heating,'and condensing the volatile low boiling liquefiable hydrocarbons produced from such low boiling hydrocarbons.

3. The process of producing volatile low boiling oils which comprises heating hydrocarbon gases under pressure in the presence of returned gases, cooling the mixture of gases and vapors formed, separating liquefiable, hydrocarbons from such mixture and returning a portion of the permanent gases for admixture'with fresh hydrocarbon gas.

In testimony whereof, I afiix my signature.

- CLIVE M. ALEXANDER. 

